Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

A novel class of chiral phosphanyl-oxazoline (PHOX) ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to...

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Bibliographic Details
Published inBeilstein journal of organic chemistry Vol. 10; no. 1; pp. 1536 - 1548
Main Authors Rubina, Marina, Sherrill, William M, Barkov, Alexey Yu, Rubin, Michael
Format Journal Article
LanguageEnglish
Published Germany Beilstein-Institut 07.07.2014
Subjects
asymmetric catalysis
Chemistry
chiral phosphine ligands
cyclopropane
Full Research Paper
Heck reaction
organophosphorus
transition metal catalysis
Heck reaction
cyclopropane
asymmetric catalysis
transition metal catalysis
organophosphorus
chiral phosphine ligands
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Summary:A novel class of chiral phosphanyl-oxazoline (PHOX) ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands.
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ISSN:1860-5397
1860-5397
DOI:10.3762/bjoc.10.158